Acylated amino alcohol quaternary ammonium derivatives of alphahalogen carboxy acid esters of oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 2,581,384 UNITED STATES PATENT- ()FFICE ACYLATEDAMINO ALCOHOL QUATERNARY AMMONIUM DERIVATIVES- OF ALPHA- HALOGEN CARBOXYACID ESTERS F OXYALKYLATED PHENOL-ALDEHYDE Melvin De Groote, UniversityCity, and Bernhard .Keiser, Webster Groves, Mo., assignors to PetroliteCorporation, Ltd., Wilmington, DeL, a corporation of' Delaware I D V vNoDrawing;

in which RC0 is a the acyl radical of a monocarboxy detergent-formingacid having at least 8 and not more than 32 carbon atoms; the aminonitrogen atom is basic; R is. an alkylene radical having at least 2 andnot more than carbon atoms; and n is a small whole number varying from 1to 10; and-the molecular weight of said compound in monomeric form beingat least 213 and not over 4,000; and the ester of an alphahalogenmonocarboxylic acid having not over 6 carbon atoms and hydrophilehydroxylated synthetic products; said-hydrophile synthetic ucts beingoxyalkylation products of (A) An alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide, andmethylglycide; and

(B) An oxyalkylation susceptible, fusible, organic solvent-soluble,water-insoluble, phenolaldehyde resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde having.not over 8 carbon atoms prodand reactive towards said phenol; saidresin being formed in the substantial absence of trifunctional phenols;said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resinmolecule ofa plurality of divalent radicals having the formula (R10)n, inwhich R1is a member selected from the class consisting of Application December13, 194s, Serial No. 65,085

Claims. (01. 260-53) ethylene radicals, propylene radicals, butylenephenolic nucleus.

' referred to as cut oil,

Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleumemulsions of the water-in-oil type, that are commonly v roily oil,emulsified oil, etc., and which comprise fine droplets ofnaturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion. This specific application is described andclaimed in our co-pending application Serial No. 65,084, filed December13, 1948, and now Patent No. 2,542,002, granted February 20, 1951. Thenew products are useful as wetting, detergent and leveling agents in thelaundry, textile and dyeing industries; as wetting agents and spreadersin the application of asphalt in road building and the like; as aflotation reagent in the flotation separation of various aqueoussuspensions containing negatively charged particles, such as sewage,coal Washing waste water, and various trade wastes and the like; asgermicides, insecticides; emulsifying agents, as, for example, forcosmetics, spray oils, water-repellent textile finishes; as lubricants,etc.

The phenol-aldehyde resins and their oxyalkylation products, which areconverted to the alpha-halogen monocarboxy acid esters used to producethe quaternary ammonium compounds of the present application aredescribed in our Patents 2,499,370, granted March 7, 1950, and

2,542,002, granted February 20, 1951, and the al-v pha-halogenmonocarboxy acid esters are described in this latter patent, andreference is made to these patents for a description of thephenol-aldehyde resins, their oxyalkylation, and their conversion toalpha-halogen monocarboxy acid esters. For specific examples of theresins, reference is made to Examples 1a through 103a of Patent2,499,370. For examples of oxyalkylated products derived from theseresins, reference is made to the tables which appear in columns 31through 46 of Patent 2,542,002. For examples of the alpha-halogenmonocarboxy acid esters of these oxyalkylatecl resins, reference is madeto Examples 10 through 390 of Patent 2,542,002.

'To produce the quaternary ammonium com pounds of the present invention,an ester of an ph fhe eeen. 9w... l 1 e se i h type exemplified byExamples through 390 of Patent 2,542,002 isf'reacted with an 'esterinedhydroxyiated amineof the kind previously referred to, to wit, a basicacylated aminoalcohol in which there is at least one occurrence of theradical RCO.(RO) n'N inoleyl triethanolamine, i. e., triethanolamineinwhich a single hydroxyl hydrogen atom has been replaced by the higheracyl radicals H00, and if one'employs a butylphenol resin andchloroacetic acid as the alpha-halogen acid to yield the ester, then andin that event, the esters containing a labile chlorine atom combinereadily with tertiary amino compounds, as herein specified, to yieldquaternary compounds. The usual method is to heat the reaction mass at135 to 165 C. for approximately 2 to 8 hours. Often the reaction iscomplete within as little as one-half an hour and may be completed ateven lower temperatures. The reaction involved, ignoring side reactions,may be illustrated as follows:

Hts

H C3H4OVOC R ounmopmogox. l on0 Hts As will be pointed out subsequently,the acylated tertiary amine may have two or more basic amino nitrogenatoms and two or more acyl. radicals. "In other words, such polyaminewould be polyfunctional towards the halogenated acid ester, and thuscould combine with'more'than 1 mole of halogentaed acidester.

Previous reference has been madeto the acyl-. ated tertiary amines bygeneral reference andby, specific example. w

' Theclass of reagentswhich are employed as reactants to combine withthe aliphatic halo-., genated carboxy acidester, consists oi aoylatedamino alcohols, in'which an acyloxy radical de-. rived from a detergentforming acidhaving from 8 to22 carbonatoms is joined to a basic nitrogenatom by a carbon atom chain, or acarbon atom chain which is interruptedat least once by an oxygen atom. The aminoalcoholsmay have more than oneamino radical, or, for that matter, more than one basic amino radical.The compounds herein contemplated as reactants are well known compoundsand are produced by conventional procedures. Stated another way, thecompounds herein contemplated' as reactants are esters oi vamino'alc'ohols which may contain etherlinliags,"

as well as more than one amino nitrogen atom.

As, a be n, P e s y: ta d t e amin pounds herein contemplated foremployment as reactants in preparing the new compositions of matter ornew compounds in the present process, are old and welllgngwn products.For convenience, and {or-purpose of brevity, reference is made to theiollowing three United States patents tq De Groote and Keiser, to wit,Nos. 2,324,488, 2,324,433 and 2,324,490, all dated July 20, 1943.aidpatente are concerned with processes ior br'ea ng water-in-oilemulsions. The demulsif ing t employed in each instance is theresultantder ved by reaction between a certain fractional e ter and anacylated aminoala I The aminoalcohols described collectively in theaforementioned three patents are used as reactants for combining with afractional acidic ester. Thus, said amingalcohols must have present analcqholiform hydronyl as part of an acyl radical, or as part of asubstituent for an amino hydrogen atom. In the instant case, suchaminoalcohols are not employed; as reactants, except as to saltformation reactions, and the hydroxyl o p. not 'iumt qn l.

aforementioned U. S. Patent No. 2,324,488 describes hydroxylatedacylated amino-ethercompoundscontaining:

(a) A radical derived from a basic hydroxyamino-ether, and said'radicalbeing of the kindcontaining at least one amino nitrogen free fromattachedaryl and amide-linked acyl radicals; said; hydroxyami'no-etherradical being further characterized by the presence or at least oneradical derived from a basic hydroxyamine and being attached by atleastoneether linkage to at least one radical selected irom the classconsisting of er ita a q yelyce ol radica s, g o radicals, polyglycolradicals, basic hydroxyamine ad isib h drq yen ine rad s. a nd:alkanolamine radicals; s'aid basic hydroxyaminoer radi bein char ter zd. y containing o m re han. 6 Q Pne Pm an (b) An acyl radical derivedfrom a detergent;- q mine o cperboxr ac a avi st least 8 ra m .v e sqnot mq sih n carbon atom saidacylated amino-ether being additionallycharacterized by the; fact that said aforemen tioned acyl radical isasubstituent for a hydrogenatom of an alcoholic hydroxyl' radical.

Aforementioned U. S; PatentNo'. 2,324,489 describes hydroxylatedacylated monoamino com;- pounds free from ether linkages,saidhydroxylated acylated amino compounds being of the following typez(ortcmgoa in which R000; represents the oxyacyl radical ri ed. m a.monebesic. d ts s n r e m n t acid; T represents a member of the classconsisting of hydrogen atom, non-hydroxy hydrocarbon radicals, andacylated radicals, obtained by replacing a hydroge n atom of thehydroxyl group of an alkylol radical by the acyl radical of a monobasiccarboxy acid having less than 8 carbon. atoms n represents a small wholenumber which isjless thaniO; m represents the numeral 1, 2 or 3; mrepresents the numeral 0, 1 or 2; and m" represents the numeral 0, l, or2; with the proviso that m plus mf plus m" equal 3. This type ofreactant is lir nited in the, instant ituation to, h e tiary amine. omou ds-i Aforementioned U. 8. Patent No. 2,324,490 describes basichydroxylated acylated polyamino compounds free from etherlinkages,saidcompounds being of the following formula:

in which n represents a small whole number varying from 2 to ;.zr is asmall whole number varying from 0 to 10; Z is a member of the-classconsisting of H, RCQR'CO, and D, in which RCO represents an acyl radicalderived from a detergent-forming monccarboxy acid; R'CO isa'n acylradical derived froma lower-moleculareweight carboxy acid having 6carbon atoms or less; and D is a member of'the class consisting ofalkyl, hydroxyalkyl, a'minoalkyl, and 'acyloxyalkylene, in whichinstance the acyl group is a member of: the class consisting of R30 andR'CO; and the acylated pclyamine is fiirther characterized by the factthat there must be presenta member of the class consisting'of (a)Acyloxyalkylene radical, in which the acyl group is RC0; and

(b) Joint occurrence of an amino radical, in which the acyl group is RC0and a hydroxyalkyl radical.

A description of certain high molal mono carboxy acids, and moreparticularly, those com monly referred to as detergent-formingmonocarboxy acids, appearsin all-three of the aforementioned U. S.patents. For convenience, the following description is substantially averbatim form of the same subject-matter as it appears in U. S. PatentNo. 2,324,490.

'-It is well known that certain monocarboxy organic acids containingeight carbon atoms or more, and not more than 32 carbon atoms, arecharacterized by the fact that they combinewith alkalis to produce soapor soaplike materials.

These detergent-forming acids include fatty acids, resin acids,petroleum acids, etc. For the sake of convenience, these acids will beindicated by the formula R.COOH. Certain derivatives ofdetergent-forming acids react with alkali to produce soap or soap-likematerials, and are the 0b.-

vious equivalent of the unchanged or unmodified detergent-forming acids.For instance, instead of fatty acids, one might employ the chlorinatedfatty acids. Instead of the resin acids, one might employ thehydrogenated resin acids. Instead of naphthenic acids, one might employbrominated naphthenic acids, etc.

., The fatty acids are of the type commonly re ferred to as higher fattyacids; and of'course, this is also true in regard to derivatives of thekind indicated, insofar that such derivatives are obtained from higherfatty acids. The petrol'eum acids include not only naturally-occurringnaphthenic acids, but also acids obtained by the oxidation of wax,paraffin, etc. Such acids may have as many as 32 carbon atoms. Forinstance, see U. S. Patent No. 2,242,837, dated May 20, 1941, toShields.

We have found that the composition of matter herein described and'employed as the break inducer of our process is preferably derived fromunsaturated fatty acids having 18 carbon atoms. Such unsaturated fattyacids include oleic acid, ricinoleic acid, linoleic acid, linolenicacid, etc. One may employ niixedfatty acids, as, for example, ,the fatty.acids obtained from hydrolysis of cottonseed oil, soyabean oil, etc.Our pre ferred"breakinducer is obtained from unsatu rated fatty acids,and more especially; unsat'u least 8 and not more than 32 carbon atoms.

and having at least .one carboxyl group or the equivalent thereof, aresuitable as detergentforming monocarboxy acids; and another analo gousclassrequally suitable is the mixture of carboxylic' acids obtained-bythe alkali treatment of alcohols :of high molecular weight formed in thecatalytic'hydrogenation of carbon monoxide; 1 is :well known, one neednot use the high mola'l carboxy acid, such as a fatty acid, for'in'troduction of the acyl group or acyloxy group.

Any suitable functional equivalent such as the acyl halide, theanhydride, ester, amide, etc., may be employed.

Attention is directed to the fact that the acylated aminoalcohols hereinemployed are obtained exclusively from hydroxylated tertiary amines anddo not include examples in which primary or secondary amines areemployed. Suitable tertiary amines which may be employed include thefollowing: Triethanolamine, diethanolalkylamines, such asdiethanolethylamine, diethanolpropylamine, etc. Other examples includediethanolmethylamine, tripropanolamine, dipropanolmethylamine,cyclohexanoldiethanoh amine, dicyclohexanolethanolamine,cyclohexyldiethanolamine, dicyclohexylethanolamine,.dicyclohexanolethylamine, benzyldiethanolamine, benzyldipropanolamine,tripentanolamine, trihexanolamine, octadecyldiethanolamine, etc.

Additional amines include ethanoldiethylamine, propanoldiethylamine,ethanoldipropylamine,- propanoldipropylamine, ethanoldicyclohexylamine,cyclohexanoldiethylamine, dibenzylethanolamine, etc." Ether typeamino-alcohols may be obtained from the above-mentioned amino-alcohols,for example, by treating them with one or more moles of an oxyalkylatingagent, such as ethylene oxide, propylene oxide, butylene oxide, glycide,etc. It is to be noted that comparable products are obtained by treatingprimary or secondary amines other than arylamines with an olefine oxide.

For practical purposes, the cheapest and the most satisfactory tertiaryamine is triethanolamine, and to a lesser extent tripropanolamine, inlight of the factthat the latter is somewhat more expensive. Thepreferred monocarboxy acids are higher fatty acids, and preferably,unsaturated higher fatty acids. Our preference is to use fatty acidshaving 12 to 18 carbon atoms, and particularly those having the lastmentioned number of carbon atoms. We have found that ricinoleic acid isparticularly desirable. It is obvious thatthe preferred monocarboxyacids, to wit, the unsaturated higher fatty acids, are mostreadilyavailable in the' form of the naturally-occurring glyceride, as,for example, castor oil, soyabean oil, sunflower seed oil, rapeseed oil,etc. The reactiontinvolving such glyceride and the selected hydroxylatedtertiary amine, such astriethanolamine, is often conducted mostconveniently at a pointapproximating th' pyrolytic point of theglycerid, such as triricinoleim' This 7 means, for example," atemperatureas high as 240 to 250 C. Under such conditions notonly. doesthe triethanolamine, for example, it used as a reactant etherize, butthe glycerol that is split may also etherize, and undoubtedly. does .toa very large extent. As a result, if one follows'the usual type ofreaction, using, for example, one

mole of triricinolein and 1, 2, 3 or 4 moles of triethanolamine perricinoleyl radical (3 to 12 moles of triethanolamine. per mole oftriricinolein) the result is, that one obtains the acylated productwhich is :a monoamine or a polyamine, depending upon the proportion ofreactants employed. "Furthermora'the glycerol whichris split of! .willalso etherize.

Our preference is to use triethanolamine along CrHeOH RCOOCQH; i NQaHrOHRCOOCQHA Nouuoomm (non imo i canon CzHe H CaH4 zHi I -aoooo,Hi

CsHeOH afito i sl mz 023 ac ooosni 00,11,011

N C 1H4 0 CJHkN c254 pinion V Example 1d 1 pound mole of ricinoleic acidis reacted with 1 pound mole of triethanolamine at approximately to 240C. for approximately 10 to 25 hours, until there is substantiallycomplete esterification.

Example 2d Ricinoleic acid in'the preceding example is replaced bymethyl naphthenate.

Example 3d Methyl abietate is substituted .for ricinoleic acid inExample 1d, preceding.

' Example 4d Ethyl 'oleate is substituted for ricinoleic. acid inExample 7 1d, preceding.

Example 5d 1 pound mole of triethanolamine is reacted with 1 pound moleof ethylene oxide and the etherized amine so obtained is substituted fortriethanolamine in Examples id to 4d, preceding.

Example 6d 1 pound mole of triethanolamine is reacted with 2 pound molesof ethylene oxide and the etherized amine so obtained is substituted fortriethanolamine in Examples 1d to 4d, preceding.

Example 7d 1 pound mole of triethanolamine is reacted with '3 poundmoles of ethylene oxide and the etherized amine so obtained issubstituted for triethanolamine in Examples 111 to 4d, preceding.

Example 8d 1 pound mole of triethanolamine is reacted with 4 to 6 poundmoles of ethylene oxide and the etherized amine so obtained issubstituted for triethanolamine in Examples 1d to id,v preceding.

Example 911 l poundv mole of ethanol diamylamine obtained by reacting 1pound mole of diamylamine with 1 pound mole of ethylene oxide isemployed in place of triethanolamine in Examples 1d to 4d, preceding.

Example 10d The same procedure is employed as in the preceding example,except that an etherized amine is obtained by treating diamylamine with2, 3 or 4 moles of ethylene oxide and such etherized amine is employedinstead of ethanol diamylamine.

Example 11d 1 pound mole of castor oil is reacted with 3 pound moles oftriethanolamine, as described in the. aforementioned U. S. Patent No.2,324,489, under the heading Intermediate Hydroxylated Amine, Example 1.

Erample 12d Thesame procedure is followed as in the preceding example,except that either 1 pound mole or 2 pound. moles of glycerol are addedto the reaction mass consisting of 1 pound mole of castor oil and 3pound moles of triethanolamine.

Example 13d.

The products obtained in Examples id to 4d, preceding, are treated withequal. molal. ratios 0! 9 Example 14d One follows the directions of U. SPatent No. 2, 3, 94, to De Groote and Keiser, dated August 18, 1942, toproduce an amine of the following composition:

CzHlO CzHa -C2H4 OH OH Such amine is substituted for trlethanolamine inthe preceding examples.

Example 1 d 1 pound mole of hydroxyethyl ethylenediamine is reacted with4 moles of ethylene oxide to give the corresponding tetrahydroxylatedderivative, Such compound is employed in place of triethanolamine in thepreceding examples.

Example 16d preceding example, except that diethylenetriamine issubstituted for ethylenediamine.

Example 18d] Amines of the following composition:

OHCgH C3H4OH iHl i i 030,11. canoe and canon OHCsHl H OH H Nmmoo (50cm,01102114 fr n 1'; 01114011 are substituted for ethylenediamine in thepreceding examples.

Example 19d In the preceding examples, where more than 1 high molal acylradical can be employed, 2 ricinoleyl radicals or the equivalent areintroduced into the polyamino alcohol.

Example 20d Unsymmetrical diphenyl diethylenetriamine is treated withethylene oxide and substituted for oxyethylated ethylenecliamine in thepreceding examples.

Example 21d Symmetrical diacetyl triethylenetetramine .is treated with 4moles of ethylene oxide andsubvstituted for oxyethylated ethylenediaminein the preceding examples. 7

Example 22d yDaminomethane; or piperidine. One may use enough of theolefine oxide, for instance, ethylene oxide, to convert all aminohydrogen atoms into .hydroxyethyl radicals, or one may employ-a greateramount so as to introduce ether linkages in addition,

'10 Example 23a The same procedure is followed as in Example 22d,preceding, except that one employs the amines described in Examples 9,10, 11 and 13 of United States Patent 2,306,329, to De Groote and IKeiser, dated December 22, 1942.

Example 24d Soyabean oil, blown soyabean oil, blown castor oil, or blownteaseed oil is substituted for castor oil in the preceding examples.

In the above examples it is obvious that free hydroxyl radicals maybepresent as part of a hydroxyalkyl radical, or as part of the acylradical 01' a fatty acid such as ricinoleic acid.

As an example of a particularly preferred type of reagent which iseffective for use in our process, the following is submitted: We preparea mixture of diamino and triamino materials which correspond essentiallyto either one of the two following type formulae:

After determining'the average molecular weight of such mixture, wecombine the same with castor oil in the proportion of 1 pound mole ofcastor oil for 3 pound moles of the mixed amines, pound mole in thelatter case being calculated on the average molecular weight asdetermined. Such mixture is heated to approximately 160- 260 C. forapproximately 6 to 25 hours, until reaction is complete, .as indicatedby the disappearance of all of the triricinolein present in the castoroil. The finished product may be used as such, but because of itsappreciable viscosity, it may be desirable to mix it with. any desiredproportion of water or. other solvent. We have found, for example, thata mixture of 20 parts of the above reagent and parts of water hasphysical properties, which are in some respects superior to those of theconcentrated material.

In summary, attention is directed to the fact that the amino compoundsherein contemplated may be monoamino or polyamino in type. They mayormay not have a free hydroxyl radical present. There must be present atleast one oc-' currence of the radical: I l

' RCO.(R'O)n'N in whichRCO is' the acyl'radical of a monocarboxydetergent forming acid having at least 8 and not more than 32 carbonatoms, and the amino nitrogen atom must be basic, i. e., free fromdirect linkage with an unsaturated or nega-,

tiveradical such asan acyl radical or an-aryl radical. The R is analkylene radical having at least two and not more thanlO carbon atoms,and preferably 2, 3 or 4 carbon atoms. The alkylene radical may beconsidered as being derived from an olefine oxide, such as thosepreviously mentioned. Additional reactive oleflne oxides are describedinU. S. Patent No. 2,208,581, to Hoeffelman, dated July 23, 1940, andinclude among othersglycidehexylene oxide,'decene oxide, etc. The"character 11. indicates a number varying from 1 to 10, but preferablyfrom 1 to 4. Recurrenceof R need not be the-same. For'instance, 1 moleof triethanolamine might be reacted with Ill 3 moles of ethyleneoxide,and the resultant prod- -.uct so obtained may be reacted with 3 moles ofbutylene oxide] The amino-alcohol so obtained could be esterified inthemanner previously de scribed. It is obvious, of course, that where n is2 or more, the product is, in essence, an esterified aminoetheralcohol,the expression etheralcohol being frequently applied to alcohols, wherea carbon atom chain is interrupted at least once by an oxygen atom.Ether linkages may appear in other positions, where there is no directunion with RCO.

For a more complete description of the amine reactants, see U. S. PatentNo. 2 366,545, dated January 2, 1945, to Morris. Broadly speaking, thedescription therein employed to describe the reactants is the following:a basic acylated aminoalcohol in which there is at least one occurrenceof the radical in which RC is the acyl radical ,of a monocarboxydetergentdorming acid having at least 8 and not more than 32 carbonatoms; the amino nitrogen atomisbasic; R is an. alkylene radical havingat least 2 and not more than carbon atoms; and n is a small whole numbervarying from 1 to 10; and the molecular weight of said compound inmonomeric form being at least 213 and not over 4,000; The reactant ofthe lowest molecular weight is obtained from dimethyl ethanolamine andoctenoic acid.

Previously, a wide variety of est'erified aminoalcohols have beendescribed under the heading oi. Example 1d, 'et seq. Two distinctclasses of esterified aminoalcohols are available commerciallymono-aminoand polyamino. In most cases such esters are preferably obtained fromunsaturated fatty acids or higher glycerides, due to the more attractivephysical property of the final derivative. The following examplesexemplify preparation of quaternary compounds from two different castoroil derivatives, the first in which castcr oil is reacted withapproximately 3 or 3.3 moles of commercial triethanolamine, and thesecond one in which castor oil is reacted with approximately 8 moles oftriethanolamine.

Example 1e 400 grams of the xylene-containing alphachloro acid esteridentified as 130 of Patent 2542002 were mixed with an equimolar amount,to wit, 138 grams of an aminoalcohol ester (a tertiary amine) obtainedby reacting one mole of triricinolein (castor oil) with '33 moles ofcommercial triethanolamine. Specifically, in the manufacture of theaminoalcohol ester the ratio employed was 932 pounds of castor oil and466 pounds of triethanolamine. The mixture was heated for 4 hours at 250C.

To the ester-tertiary amine mixture, there was added an amount of xyleneequal in weight to about of the tertiary amine. In the instant case thiswas grams. A little xylene was lost during the subsequent reflux period.The experiments were conducted so that in the majority of cases thefinal product contained approximately xylene. If desired, this xylenecould be eliminated by evaporation, or

vacuum distillation. In the use ofthepl for demulsification it isconvenient to have the xylene present so as to give a non-viscous liquidwhich can be handled easily.

The two reactants were refluxed at the boiling point of xylene(approximately 140- 0.) 0 1 2 99 xylene.

' soluble liquid.

4 hours. Tests in this kind of reaction have invariably indicated that.the reaction was .com-

.plete in lessthan 2' hours and sometimes in as Emdmple 2e The procedureemployed was the same as that in Example 1e, except that 400 grams ofthe ester identified as of Patent 2,542,002 were reacted with 139 gramsof the tertiary amine previously described specifically under theheading of Example 1c. The product contained 38.5% xylene. This Was aviscous, deep-ambercolored water-soluble liquid.

Example 3e V The procedure employedwas the same as that in Example 1e,except that 400 grams of the ester identified as 20 of Patent 2,542,002were reacted with .189 grains of the tertiary amine previously describedspecifically under the heading of Example 12. The product contained43.7% xylene, and wasa somewhat viscous, deep amber-coloredwater-soluble liquid.

Example 46 The procedure employed was the same as that in Example 1e,except 'thatk400 grams of the ester identified as of Patent 2,542,002were reacted with 157 grams of the tertiary amine previously describedspecifically under the heading of Example 1c. The product contained44.7% xylene, and was a viscous, deep ambercolored water-soluble liquid.

' Example 5e The procedure employed was the same as tha in Example 1e,except that 400 grams of the ester identified as 180 of Patent 2,542,002were reacted with grams of the tertiary amine previously describedspecifically under the head.- ing of Example 1c. The product contained37.6% xylene, and was a viscous, deep-ambercolored water-soluble liquid.

Example 6e The procedure employed was the same as that in Example 1e,except that 400 grams of the ester identified as 40 of Patent 2,542,002were reacted with 129 grams of the tertiary amine previously describedspecifically under the heading of Example la. 'The product contained35.4% xylene, and was a viscous deep ambercolored water-soluble liquid.

Erample 8e "The same procedure was followed as in Example "1e, exceptthat the tertiary amine employed was an aminoalcohol obtained byreacting one mole of triricinolein with 8 moles of'coinm'er cialtriethanolamine. Specifically, in the manufacture of this particularamino alcohol ester, there were employed 932 pounds of castor oil and1200 pounds of triethanolamine. The mixture was heated for 4 hours at250 C. The specific reactant mixture was 400 grams of the esterdescribed as 240 and 135 grams of the tertiary amine reactant describedimmediately preceding. As previously noted, the entire procedure wasidentical with that described under Example 1e. The resultant productcontained 34% xylene. It was a viscous, deep amber-colored liquid whichwas water-soluble.

Example 9e The procedure employed was the same as that in Example 1e,except that 400 grams of the ester identified as 100 of Patent 2,542,002were reacted with 114 grams of the tertiary amine previously describedspecifically under the heading of Ex ample 1e. The product contained37.2% xylene and was a non-viscous, deep amber-colored water-solubleliquid.

Example 109 The procedure employed was the same as that in Example 16,except that 400 grams of the ester identified as 140 of Patent 2,542,002were reacted with 144 grams of the tertiary amine previously describedspecifically under the heading 'qfExample 1c. The product contained33.2% xylene and was a non-viscous, deep amber-colored wa ter-solubleliquid.

Example Us Y 7 The procedure employed was the same as that in Example1e, except that 400 grams of the ester identified as 90 of Patent2,542,002 were reacted with 143 grams of the tertiary amine previouslydescribed specifically under the heading of Example 1e. The productcontained 37% xylene and was a non-viscous, deep amber-coloredwater-soluble liquid.

Example 126 The procedure employed was the same'as that in Example 1e,except that 400 grams of the ester identified as 20c of Patent 2,542,002were reacted with 120 grams of the tertiary amine previously K describedspecifically under the heading of Example 1e. The product contained36.4% xylene and was a non-viscous, .deep amber-colored water-solubleliquid.

Example 14a The procedure employed was the same as that in Example 1e,except that 400 grams of the ester identified as 3c of Patent 2,542,002were reacted with 151 grams of the tertiary amine previously describedspecifically under the heading of Ex:

ample la. The product contained 36% xylene and was a non-viscous, deepamber colored water-SOlllble liquid. V

i 14' Example 15c The procedure employed was the same as that in Example1e, except that 400grams of the ester identified as 230 of Patent2,542,002 were reacted with 206 grams of the tertiary amine previouslydescribed specifically under the heading of Ex ample 1e. The productcontained 30.4% xylene and was a non-viscous, deep amber-coloredwater-soluble liquid.

Example 16a The procedure employed was the same as that in Example 1e,except that 400 grams of the ester identified as 250 .of Patent2,542,002 were reacted with 133 grams of the tertiary amine previouslydescribed specifically under the heading of Example 1e. The productcontained 33.4% xylene and was a non-viscous, deep amber-colored,water-soluble liquid;

Having thus described our invention, what we claim and desire to secureby Letters Patent is:

1'. A quaternary ammonium compound" obtained by reaction between a basicacylated aminoalcohol, in which there is at least one occurrence of theradical j in which RC0 is the acyl radical of a monocarboxydetergent-forming acid having at least 8 and not more than 32 carbonatoms; the amino nitrogen atom is tertiary and basic; R is an alkyleneradical having at least 2 and not more than 10 carbon atoms; and n is asmall whole number varying from i to 10; and the molecular weight ofsaid compound in monomeric form being at least 213 and not over 4,000;and an ester in which the acyl radical is that of an alphahalogenmonocarboxylic acid having not over 6 carbon atoms and composed ofcarbon, hydrogen, oxygen and halogen and the alcohollc radical is thatof certain hydrophile polyhydric synthetic products; said hydrophilesynthetic products being oxyalkylation products of (A) an alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from theclass consisting of ethylene oxide, propylene oxide, butylene'oxide,glycide and methylglycide; and (B) an oxyalkylation-susceptible,fusible, organic solvent-soluble, water-insoluble, phenol-aldehyderesin; said resin being derived by reaction between a difunctionalmonohydric phenol and an aldehyde having not over 8 carbon atoms andhaving one functional group reactive towards said phenol; said resinbeing formed in the substantial-absence of phes nols of functionalitygreater than no] being of the formula:

l. i OH radicals,hydroxypropylene' radicals, and hydrox= 'ybutyleneradicals, and n is a numeral varying froml' to'20; with the. provisothat at least. 2 moles of'alkylene oxide be introduced for eachphenolicnucleus... a

two; said phe-v swim 15 2. A quaternary ammonium compound obtam d, by ra on. w e ANN-$ a yla aminoalcohol, in which there is at least pileoccurrence of the radical RCO.(OR'-)wN in which RC is the acyl radicalof a mono carboxy detergent-forming acid having at least 8'and not morethan 32 carbon atoms; the amino nitrogen atom is tertiary and basic; R.is an alkylene radical having at least 2 and not more than 10.carb0natoms; and n is a small whole number varying from 1 .to and themolecular weight of said compound in monomeric form be ing at least 213and not over 4,000; and a chloroacetate of certain hydrophile polyhydricsynthetic products; said hydrophile synthetic productsbe'lingox'yalkylation products of (A) an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butyiene oxide, glycide andmethylglycide; and (B) an oxyalkylahon-susceptible, fusible, organicsolvent-soluble, water-insoluble phenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and having one functional groupreactive towards said phenol; said resin being formed in the substantialabsence of phenols of functionality greater than two; said phenol beingof the'formula;

. V DH .l

in which R is a hydrocarbonradical having at least 4 and not more than'12 carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (RiOM, in which R1 is a member selected fromthe class consisting of ethylene radicals, propylene radicals, butyleneradicals, hydroxypropylene radicals, and hydrox ybutylene radicals, andn is a numeralvarying from 1 to with the proviso that at least 2 molesof alkylene oxide be introduced for each phenolic nucleus; and with thefinal proviso that the hydrophile properties of the ultimate quaternaryammonium compound as well as the ox'yal kylated resin in anequal weightof xylene are suilicient'to produce an emulsion-whensaid "xvlenesolution is shaken vigorously I with one to three volumes of water. 7 i

3. A quaternary ammonium compound obtained by reaction between'a basicacylated aminoalcohol in which there is at least one occurrence of theradical ing at least 213. and not'over 44000; and-a chiOrO-x acetate ofcertain hydrophilexpoiyhydric syn? thetic products; said hydmphilesynthetic prod-i uctsbeing oxyethylation products. of (A) ethyl-v oneoxide. and (B) an oxyethylation-susceptible,

functionality greater than two; said phenol being or the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyethylated resin being characterized by the introduction into theresin molecule'at the phenolic hydroxyls of a plurality of divalent radicals having the formula (C2H40)n; wherein n is a numeral varying from 1to 20; with the proviso that at least 2 moles of ethylene oxide beintroduced for each phenolic nucleus; and with the final proviso thatthe hydrophile properties of the ultimate quaternary ammonium compoundas well as the oxyethylated resin in an equal weight of xylene aresufiicient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of water. v p H 4. A quaternaryammonium compound obtained by reaction between a basic acylated ami-.noalcohol in which there is at least one occurrence of the radical inwhich RC0 is the acyl radical of a, monocarboxy detergent-forming acidhaving at least 8 and not more than 32 carbon atoms; the amino nitrogenatom is tertiary and basic; R is an alkylene radical having at least 2and not more than 10 carbon atoms; and n is a small whole number varyingfrom 1 to 10; and the molecular weight of said compound inmonomeric formbeing at least 213 and not over 4,000; and a chloroacetate of certainhydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) anoxyethylation-susceptible, fusible, organic solvent-soluble,water-insoluble, low-stage phenol-aldehyde resin having an averagemolecular weight corresponding to at least 3 and not over .7 phenolicnuclei per resin molecule; said resin being derived by reaction between2, difunctional monohydric phenol and formaldehyde; said resin beingformed in the substantial absence of phenolsof functionality greaterthan two: said phenol being of the formula: I

with the proviso that at least 2 moles of ethylene oxide be introducedfor each phenolic nucleus; and with the final proviso that thehydrophile properties of the ultimate quaternary ammonium compound aswell as the oxyethylated resin in an equal weight of xylene aresufficient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of water.

5. The product of claim 4, wherein R is substituted in the para.position.

6. The product of claim 4, wherein R is a butyl radical substituted inthe para position.

7. The product of claim 4, wherein R is an amyl radical substituted inthe para position.

8. The

product of claim 4, wherein R is a nonyl radical substituted in the paraposition.

MELVIN DE GROOTE. BERN HARD KEISER.

REFERENCES CITED Number UNITED STATES PATENTS Name Date De Groote Mar.7, 1950

1. A QUATERNARY AMMONIUM COMPOUND OBTAINED BY REACTION BETWEEN A BASICACYLATED AMINOALCOHOL, IN WHICH THERE IS AT LEAST ONE OCCURRENCE OF THERADICAL